Copper complex compounds of disazo dyestuffs of the stilbene series



Patented Oct. 10, 1939 UNITED STATES PAT EN-T QFFF I CE COPPER COMPLEX COIVIPOUNDS; OF DISAZO DYESTIJFFS OF THE;.STILBENE SERIES Hans Schindhelm,

Frankfort-on-the Main- Fechenheim, Germany, assignor, to General Aniline Works, Inc.,

New York, N. Y., a corporation of Delaware No Drawing. Application April 15, 1938', Serial No. 202,291. In Germany Aprilx19, 1937 4 Claims.

SOaH SOsH wherein acyl means the radicle of a carboxylic acid selected from the group consisting of the aliphatic and the benzene series and A and B stand for sulfonated radicles .of the naphthalene series which contain in o-position to the azo 15 group a group capable of beingv metallized.

The aforesaid new copper complex compounds are obtained according to the present invention for instance by the following process of manufacture. 4"-nitro-.4r aminostilbene-2,2-disulfonic acid is acylated, then the nitro group of the 4-nitro-4-acy1aminostilbene-2,2-disulfonic acid obtained is reduced, the 4-amino-4-acylaminostilbene2,2'-disulfonic acid formed is diazotized and its diazo compound is combined with a diazotizable amine of the naphthalene series containing inc-position to the diazotizable amino group a group capable of being. metallized. The amino azodyestufi thus obtained is further diazotized and the diazo compound formed is combined with a compound of thenaphthalene series containing in o-position to the coupling position a group capable of being metallized; Then the disazodyestufi formed is converted in the usual manner into the corresponding coppeircomplex compound.

The single stages of the aforesaid process may also be performed in another. sequence. Thus, for example, at first a,nitrostilbene-disazodyestuff may be prepared the nitro group of which is then reduced to the amino group. I-Iereupon the aminostilbene-disazodyestuff formed is acylated and then converted into the corresponding copper complex compound.

vegetable fibers green to greenish gray shades of excellent fastness to light.

In order to' further illustrate my invention the following examples are given, the parts being by Weight and all: temperatures in degrees centirade.

Example 1 336 parts of l-nitroi-aminostilbene-2,2-di-- sulfonic acid are dissolved in about 3800 parts of water. The solution is neutralized and then 140 parts of acetic acid anhydride are added, while stirring. When theacylation iscomplete, the solution is heated to about 90 and about 2000parts of sodium chloride are added. The 4-nitro-4- acetylaminostilbene-2,2-disu1ionic acid formed precipitates fromthe solution while cooling. It is filtered off and washed with an aqueous sodium chloride solution. Then itis reduced in the usual manner by means of iron and acetic acid.

The l-aminol-acetylaminostilbene-2,2 di sulfonic acid thus obtained is diazotized in the usual manner and the diazo compound formed is combined with an aqueous solution of 270 parts of 1-amino-2-ethoxynaphthalene-6sulfonic acid in the presence of :sodium carbonate. Whenqthe combination is complete, the aminoazodyestufi formed is isolated, purified and further diazotized. The diazo compound obtained is combined with an aqueous solution of 310 parts ofthe sodium salt of 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid containing about l-percent by'volume of pyridine. The disazodyestufi thus obtained is precipitated by the addition of sodium chloride, filtered off and, if necessary, purifiedby dissolving it in water and reprecipitatin g it from this solution. Then it is dissolved in water, the aqueous solution of 300 parts of crystallized copper sulfate is added and the mixture isheated to boiling for about '78 hours in the presence of sodium acetate, whereby the formation of the copper complex compound of the-formula:

SOsNa 45 NaQaS NH to EN CH=CH N=N N=N (g H! 00 SO N 0 N9. 0

The new copper complex compounds prepared according tothe present invention are dyestuffs 55 of valuable tinctorial properties. They yield on is performed. It is, when dry, a dark powder, soluble in concentrated sulfuric acid with a greenish-gray and in water with a bluish-gray color, dyeing cotton grayish-green shades of excellent fastness to light.

By employing instead of the sodium salt of 2- acetylamino- 5 -hydroxynaphtha1ene- '7 -sulfonic acid in the above example the corresponding amount of the sodium salt of 2-succinoylamino-5- hydroxynaphtha1ene-7-sulfonic acid, a copper complex compound of the formula:

ing copper complex compound in an analogous NaO|S IIIH C O HN- CH=CH N=N N=N I C O I SOxNa SOaNa O I OH: CH: I

Cu O O OH is Obtained. It is, when dry, a dark powder, 501- uble in concentrated sulfuric acid with a greenish-gray and in water with a bluish-gray color,

manner as described in Example 1. The copper complex compound thus obtained corresponds to the formula:

SOaNa NaOzS NH S OzNa BO|Na O I dyeing cotton greenish-gray shades of excellent fastness to light.

Similar valuable copper complex compounds are obtained by employing as end component for the manufacture of the stilbene disazodyestuff instead of 2-acetylamino-5-hydroxynaphthalene- 7-sulfonic acid analogous compounds such as for example 2-benzoylamino-5-hydroxynaphthalene- 7-sulfonic acid, 2-(2'-carboxybenzoylamino)-5- hydroxynaphthalene-7-sulfonic acid, 2-chloracetylamino-5-hydroxynaphthalene-7-sulfonic acid, Z-methoxyacetylamino-S-hydroxynaphthalene-7- sulfonic acid and the like.

Example 2 336 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid are dissolved in about 4000 parts of water. The solution is neutralized and mixed with a concentrated aqueous solution of 200 parts of sodium carbonate. Then 130 parts of benzoylchloride are slowly added during about one hour, while stirring, at about 15-25. When the acylation is complete, the 4-nitro-4'-benzoylaminostilbene-2,2'-disulfonic acid formed is precipitated by the addition of sodium chloride, filtered 01f, purified and then reduced in the usual manner by means of iron and acetic acid.

The 4-amino-4'-benzoylaminostilbene-2,2disulfonic acid thus obtained is diazotized in the usual manner and the diazo compound formed is combined with an aqueous solution of 267 parts of l-amino-Z-ethoxynaphthalene-7-sulfonic acid in the presence of sodium carbonate. When the combination is complete, the aminoazo dyestufi formed is separated and further diazotized. The

f C11 NaOOC It is, when dry, a dark powder, soluble in concentrated sulfuric acid with a green and in water with a bluish-green color, dyeing vegetable fibers greenish-gray shades of good fastness to light.

Similar valuable dyestuffs are obtained by replacing benzoylchloride, in the above example, by its substitution derivatives such as, for example, 3-methoxybenzoylchloride, i-chlorobenzoylchloride and the like.

By employing as end component for the manufacture of the disazodyestuif instead of 2-(3- carboxyphenylamino) -5- hydroxynaphthalene -7- sulfonic acid other compounds of the naphthalene series containing in o-position to the coupling position a group capable of being metallized, analogous dyestuffs distinguished by similar good properties are obtained.

I claim:

1. Copper complex compounds of disazodyestullifs of the stilbene series of the general form a:

wherein acyl means the radicle of a carboxylic acid selected from the group consisting of the aliphatic and the benzene series and A and B stand for sulfonated radicles of the naphthalene series which contain in o-position to the azo group a group capable of being metallized, which copper complex compounds dye vegetable fibers green to greenish gray shades of excellent fastness to light.

2. The copper complex compound of the formula:

which is, when dry, a dark powder, soluble in concentrated sulfuric acid with a greenish-gray and in water with a bluish-gray color, dyeing vegetable fibers grayish-green shades of excellent fastness to light.

[ SOzNa with a bluish-gray color, dyeing vegetable fibers greenish-gray shades of excellent fastness to light.

4. The copper complex compound of the formula:

SOzNa 3. The copper complex compound of the formula:

S O 3N8 I aNa SOaNa O O which is a dark powder, soluble in concentrated sulfuric acid With a greenish-gray and in water NaOaS NaOOO which is a dark powder, soluble in concentrated sulfuric acid with a green and in Water with a bluish green color, dyeing vegetable fibers greenish gray shades of good fastness to light.

HANS SCHINDHELM. 

